Waterless skin cleaner and process for producing the same



Unite States This invention relates to waterless skin cleaner and a process for producing the same. In particular, it is related to a skin cleaner emulsion having thixotropic and fast breaking qualities, and is a continuation-in-part of Serial No. 516,775, filed June 20, 1955, now abandoned.

The skin cleaner emulsion is waterless in the sense that when used by workers no water need be employed for washing or rinsing, as when soap and water is used. The particular application of the cleaner finds its principal use by industrial workers and mechanics who frequently soil their hands with grease, grime and related soils, and contaminants which are not readily laved with ordinary soap and water. This skin cleaner emulsion has a very high cleaning power for such contaminants and, in addition, has the advantage of being able to clean the skin without the aid of water.

The skin cleaner emulsion of this invention is in the form of a cream or paste, and is thixotropic or pseudoplastic in the sense that, when it is in a stationary state, it is thick and viscous, but when subjected to shear, it reverts to a liquid state. Thus, when applied to the skin, the massaging of the cleaner on the skin effects shear which quickly reduces it to a liquid. This liquid state imparts lubricity which dissolves, emulsifies and mechanically sweeps the contaminants from the skin.

The fast breaking quality resides in the fact that when the cleaner is transformed to fluid state and contacts the contaminants, such as grease and grime, the emulsion is irrevocably destabilized in that it is no longer thixotropic and will not revert to the viscous form of the cream or paste. The resulting fluid mass may then readily be wiped off with the contaminants leaving the skin clean.

Accordingly, it is a primary object of this invention to provide a skin cleaner emulsion which does not require water in use and has thixotropic and fast breaking qualities.

Another object of this invention is to provide a bland and odorless skin cleaner emulsion having thixotropic and fast breaking qualities in which the emulsion is stable against the influence of time, temperature, and normal storage conditions, and has high cleaning power.

Still a further object of the invention is to provide a skin cleaner emulsion which does not require water for use, can be dispensed in the form of a viscous cream or paste, can be used by a worker for washing grime and grease with no toxic effects on the skin, and has no unpleasant aroma.

Yet another object of the invention is to provide a waterless skin cleaner emulsion having thixotropic and fast breaking qualities in a simply controlled process from readily available materials.

Further objects of this invention will appear in the detailed description which follows and will be further apparent to those skilled in the art.

The skin cleaner emulsion of this invention achieves its cleaning power without the use of soaps which are alkaline in nature and, when used without an adequate water rinse, constitute a potential skin hazard. The skin cleaning power in the emulsion is achieved by imparting active emulsifying power to bland, cosmetic-type mineral oil. The cleaner preferably does not contain kerosene or petroleum naphthas in the kerosene range, which however may be employed for industrial and other uses where atent emulsifier, and particularly the polyoxyethylene' esters of 3,277,013 Patented Oct. 4-, 1966 their low cost makes this of advantage, and the cleaning is achieved by a gentle emulsifying action coupled with thle restricted favorable solvency performance of mineral or.

Mineral oil is an efficient solvent for grease and grime which constitute the principal soil contaminants on the hands of industrial workers and mechanics. This mineral oil is at the same time a poor solvent for lipids and other physiological components of the skin so that the cleaner achieves a maximum effect on the contaminants coupled with a minimum defatting action of the skin.

It has been found in this invention that a nonionic fatty acids in which the hydrophilic ethylene oxide chain attached to a fatty acid, can be used where the length is such as to impart such characteristics as to be sparingly soluble in mineral oil at room temperature (al though soluble in hot mineral oil), and dispersible in water, but not completely soluble. These esters are exceedingly effective in imparting the stability and, in part, the relatively high viscosity desired. The ethylene oxide content to achieve the desired results is preferably about five1 mols and can be within the range of two to twenty mo s.

The fatty acids in the polyoxethylene esters may be both saturated and unsaturated within the range of 12 to 22 carbon atoms; and, as examples, palmitic and stearic acids may be used with advantage when coupled with the proper molal content of ethylene oxide. As an example, it has been found in this invention that the ethylene oxide fatty acid ester may be an ester containing stearic acid in combination with five mols of ethylene oxide according to the following structural formula, where X equals 5 mols, and R is an alkyl group of 17 carbon atoms.

Such an ester with ethylene oxide may be Ethofat 60/15 produced by the Armour Chemical Company, of Chicago.

For the purpose of imparting added fast breaking qualities to the skin cleaner emulsion, small quantities are used of a tertiary amine having one fatty alkyl group and two polyoxyethylene groups substituted on the amino nitrogen. The ethylene oxide is preferably about 5 mols, and the fatty alkyl group is, for example, one derived from tallow acids. A structural formula is as indicated below where X and Y equal 5 mols.

X=2 /2 mols Y=2 /2 mols R=Tallow acid The tertiary amine of the type indicated above imparts, in part, the fast breaking quality and transforms the emulsion more rapidly to a liquid state on the shear effected by massaging. The cleaner also shows increased thermal stability and exhibits increased viscosity in the stationary state. Such a tertiary amine of the type above described is exemplified by Ethomeen T/ 15 manufactured by Armour Chemical Company. The tertiary amine is of further value in reacting with a synthetic hydrophilic colloid polymer, which is further described below, to produce the desired effects in the emulsion composition.

Small quantities of the tertiary amine must be utilized since amounts over 0.10% cause a film formation on the skin when used. For stability purposes, up to 2% can be utilized where the deleterious effects of the film formation are not important. Preferably, however, in this emulsion amounts of 0.08% are utilized, and this can extend downwardly to the range of 0.035%. This component may be omitted under some circumstances where a high degree of stability and fast break are not required.

A synthetic hydrophilic acid polymer colloid is utilized for its thickening and gel forming efliciency and to impart relatively high viscosity and stability. Of special advantage is a long chain cross linked copolymer of polymethylene nature with double bond linkage which is carbon-to-carbon linked. This copolymer supports frequent carboxylic acid radicals. The basic monomer employed in this colloid is essentially acrylic acid or its homologues copolymerized with a poly allyl sucrose. This copolymer is about 99% by weight of glacial acrylic acid and about 1% by Weight of a poly allyl sucrose in which the sucrose molecule has from 5 to 6 allyl groups. The chain of the polymer is substantially linked through the double bond. The molecular weight of this synthetic hydrophilic acid polymer colloid is quite large, and, for example, may be in excess of 150,000. As an example, Carbopol 934, described in the service bulletin GC-20 of March, 1954, by B. F. Goodrich Chemical Company, can be utilized. This colloid is a water-sensitive gum which has gel-forming qualities and is acid in nature, being transformed into a clear stable gel when neutralized. It is resistant to aging and is stable to temperature variation and degradation by bacterial or fungal attack. The colloid thickening agent is preferably employed in the amount of about 0.7 to 2.1% by weight of the water, although this may be varied where thinner or thicker emulsions are desired, respectively.

The above components are the major ingredients of the skin cleanser emulsion which is prepared with a goodly amount of water, as will be further described below. However, it has been found to be of high advantage to include a sarcosine, such as oleyl sarcosine free acid, which imparts an adjuvantive value in inhibiting corrosion, which might otherwise occur in dispersers and metal containers. This sarcosine acid is compatible with the components utilized in the skin cleaner and has been found to be quite favorable. Further, corrision inhibiting characteristics, especially in the vapor phase, may be imparted to the cleanser by including small quantities of amine nitrites, such as Z-hydroxy-propylamine nitrite in the product.

Also, to prevent evaporation, a glycol is utilized in the cleaner composition. These glycols, of course, must be dermatologically innocuous, and, as an example, propylene glycol has been found to be of advantage when over 5% by weight is used. Likewise, diethylene glycol may be advantageously employed.

To effect the gelling of the hydrophilic acid polymer colloid, an alkali such as 20% sodium hydroxide is used. This causes the viscosity to increase instantly and transforms the liquid solution to a pasty state. The alkali preferentially neutralizes the hydrophilic colloid acid polymer, and the resultant cleaner composition has a pH of about 6 corresponding to the pH of the skin, and may be within the general range of 5 to 7 in pH, although this may be varied where desired. This gentle acidity removes far less natural skin fats and related dermal and epidermal constituents than conventional cleaners operating with soaps or detergents in the alkaline range above the pH of 7. Also, the normal acidity of the skin is not disturbed so that the acid mantel may continue to act as a bacteriocide.

The skin cleaner emulsions with the above ingredients, and prepared to the formulations such as typified below, have outstanding thermal stability, even under prolonged exposure at 150 F. and have not deteriorated by prolonged exposure to sub-freezing temperatures. Further the cleaner resists any tendency to cream or otherwise separate on aging, and has no changes in viscosity or tendency to hydrolize on standing, even under appreciable and extensive periods of time. The cleaner is pure white in color, which does not change under the influence of time or exposure to sunlight.

sitions set forth.

EXAMPLE 1 Material Trade Name Amount Percent Mineral oil, viscosity Eureka White Oil, 40 gal 1 35. 7

50-60 second Saybolt. (Sjtandard Oil 0. Reaction product of Ethofat 60/15, 10 lbs 1. 3

stearic acid and 5 Armour Chem. moles of ethylene Co. oxide. Reaction product of pri- Ethomeen '1l15, 4.68 02. (av.) O. 04

mary amine derived Armour Chem. "'from tallow fatty Co.

acids and 5 moles of ethylene oxide. Oleyl sarcosine free SarkosylO, Geigy 9.36 oz 0.07

acid. Chem. 00. Synthetic hydrophilic Carbopol 934, B. 8 lb. 6 oz 1.07

colloid acid polymer. F. Goodrich Chemical 00. Water 50. 2 Propylene glycol 9. 63 Sodium hydroxide 20% 1. 93 solution. Perfume 7.75 Ii. oz 0.06

Procedure In the process for the formulation of Example 1, the reaction product of stearic acid and 5 moles of ethylene oxide, the reaction product of primary amine derived from tallow fatty acids and 5 moles of ethylene oxide, and the sarcosine are melted together at 40 to 60 C. The resultant mixture is added to the mineral oil, which has been previously heated to about 65 and 70 C. In a separate vessel Water is charged and the synthetic hydrophilic colloid is slowly added thereto with agitation. The water and synthetic hydrophilic colloid are mixed until the acid polymer is completely dissolved. Then to this solution of the acid polymer, propylene glycol is added and the mixture is heated to between 65 and 70. Subsequently the mineral oil phase is agitated, and the water phase containing the synthetic hydrophilic colloid is slowly and steadily added to it to form a white emulsion.

The emulsion is agitated at approximately 66 C., and to it is slowly added the sodium hydroxide solution, which has been previously heated to 67 C. The sodium hydroxide neutralizes in situ the acid polymer to form a well bodied gel, and the pH of the mass rises to about 6.

The resultant emulsion is cooled to approximately 40 C. and perfume is added with continued mixing for thorough dispersion. In the last stage the entire product is passed through a colloid mill or a homogenizer to complete the manufacture of the skin cleaner emulsion and bring back the reversed emulsion.

EXAMPLE 2 Material Trade Name Amount Percent Mineral oil, viscosity Eureka White Oil, 400 cc 35. 8

50-60 second Saybolt. @tandard Oil 0. Reaction product of Ethotat 60/15, 12 grams 1. 3

stearic acid and 5 Armour Chem. moles of ethylene Co. oxide. Synthetic hydrophilic Carbopol 934, B. 10 grams 1. 1

colloid acid polymer. F. Goodrich Chemical Co. Diethylene glycol grams 5. 3 Water. 508 cc 54. 4 20% Solution sodium 20 grams 2. 1

hydroxide.

Procedure The reaction product of stearic acid and 5 moles of ethylene oxide are dissolved in the white oil and brought to 65 C. The synthetic hydrophilic acid polymer is dissolved in the water, heated to 67 C., and added into the oil phase with agitation. As the agitation is continued diethylene glycol is added to the water phase. The water and oil solutions are then mixed together, and lastly, sodium hydroxide is added with continued agitation and a maintenance of the mixture at 60 C.

In this example, the colloid mill or a homogenizer is not employed. For some applications where a substantial storage period is not contemplated, this has been found satisfactory. However, where storage for any considerable period of time is contemplated, the shear effected by a colloid mill or homogenizer should be utilized for higher viscosity and better stability. This operation has also been found advantageous to enhance the whiteness of the product.

EXAMPLE 3 Material Trade Name Amount Percent Mineral oil, viscosity Eureka White Oil, 400 cc 35.8

50-55 second Saybolt. gtandard Oil Reaction product of Ethofat 60/15, 12 grams 1.3

- stearic acid and 5 Armour Chem.

moles of ethylene Co.

oxide. Reaction product of pri- Ethomeen T/15, 2 grams 0. 6

mary amine derived Armour Chem.

from tallow fatty Co.

acids and 5 moles of ethylene oxide. Synthetic hydrophilic Carbopol 934, B. grams 0. 8

colloid acid polymer. F. Goodrich Chemical Co.

Diethylene glycol 50 grams 5. 3 Water 513 cc 54.7 Sodium hydroxide 20% 14 grams 1.

solution Procedure The mineral oil, reaction product of stearic acid and 5 moles of ethylene oxide and reaction product of primary amine derived from .tallow fatty acids and 5 moles of ethylene oxide are mixed together and brought together at 70 C. The hydrophilic colloid is then mixed and dissolved in the water with agitation to which is subsequently added the diethylene glycol. This latter mixture is brought to 72 C. and added to the oil phase with agitation. The resultant mixture is cooled to 60 C. and sodium hydroxide is slowly added. The batch is then passed through the colloid mill or a homogenizer and is ready for use.

EXAMPLE 4 PART A Percent Mineral oil 20.0 Lanolin 0.25 Cetyl alcohol 0.80

PART B Water 41.47 Carbitol (diethylene glycol monoethyl ether) 20.00 Propylene glycol 10.00 Polytergent G-300 (ethylene oxide nonylphenol non-ionic) 3.00 Carbopol 934 0.70 Bentonite 1.00 Titanium dioxide 1.00 Triethanol amine 1.17 Corrosion inhibitor 0.50 Perfume 0.11

Method Mix Part A and warm to 100 F. In another vessel add the water, Carbitol, propylene glycol and Polytergent G-300 which is a non-ionic emulsifying agent. With strong mixing sift the Carbopol 934 into the water. Completely disperse the Carbopol, then sift in Bent-onite and Titanium Dioxide. Add Part A into Part B with mixing. Then add the triethanol amine, the corrosion inhibitor and the perfume. Continue mixting until product is smooth and creamy. This product is very effective for the removal of hectograph ink as well as for the removal Combine Part A in vessel with mixing and warm to F. maximum. In second vessel add water, Polytergent G-300 and propylene glycol. With strong mixing sift Carbopol 934 into water. Disperse thoroughly. Add Part B into Part A with mixing. Dissolve caustic in water to make Part C. Add this Part C into mixing A and B. Continue mixing until a smooth creamy product results. This product is very effective on paints and greasy soils and a variety of others.

EXAMPLE 6 PART A Percent LEP solvent (Stoddard Type) 20.0 Lanolin 0.5 Ethofat 60/15 1.2 Perfume 0.1 Corrosion inhibitor 0.5 Sarkosyl-O 0.1

PART B Water 71.85 Propylene glycol 2.0 Polytergent G300 1.0 Carbopol 934 0.5

PART C Caustic Soda 0.25 Water 2.0

Method Mix Part A with temperature of approximately 90 F. In separate container place water, propylene glycol and Polytergent G-300. With strong agitation sift Carbopol 934 into the water and completely disperse. Dissolve caustic soda in water, Add Part A into Part B with mixing and then add Part C. Continue mixing to make a smooth, creamy lotion. This product is quite effective on light soils and is very stable.

EXAMPLE 7 Percent Water 83.22 Carbopol 934 0.045 Stearic acid 4.0 Lantrol (a lanolin fraction) 1.40

7 EXAMPLE 7Continued Percent Cetyl alcohol 1.00 Mineral oil 3.30 Diethylene glycol monoethyl ether solvent 4.80 Hexachlorophene 0.40 Butyl parahydroxybenzoate 0.10 Butylated hydroxytoluene 0.01 Triethanol amine 0.25 Triethanol amine 1.25 Color 0.018 Perfume 0.20

Method Heat the water to 140 F. With strong agitation, sift the Carbopol into the water. When completely dispersed use stirrer mixing and slowly add the 0.25% triethanol amine into the water. In a separate vessel combine all of the items from stearic acid through butylated hydroxytoluene. Heat to 135 F. maximum with mixing until all are dissolved. Then add the 1.25% triethanol amine. Add this oil mixture into the water, mix rapidly for ten minutes while cooling, then mix slowly until temperature is 110 F. Add the color and perfume, then mix slowly for an additional twenty minutes. This product uses an anionic emulsifying agent obtained by reacting the stearic acid with the triethanol amine and provides a very effective lanolin lotion.

EXAMPLE 8 Percent Mineral oil 40 Ethofat 60/15 6.0

Water 52.98 Carbopol 934 0.75 Sodium hydroxide 0.27

Method EXAMPLE 9 Percent Mineral oil 35.8 Ninol AA 62 Extra (diethanol amine condensate of methyl .laurate) 1.5 Carbopol 934 1.1 Diethylene glycol 5.3

Water 54.2 20% sodium hydroxide 2.1

(a) Dissolve and disperse Ninol AA 62 Extra in the mineral oil with warming to eifect solution.

(b) Using constant agitation, dissolve the Carbopol 934 in water and diethylene glycol. Add Part A into Part B slowly with constant agitation. Then add 20% sodium hydroxide slowly with continued agitation.

This is approximately the same as Example 2 of this patent application with Ninol AA 62 Extra substituted for the Ethofat. Ninol AA 62 Extra is a non-ionic emulsifying agent defined as a diethanol amine condensate of methyl laurate, normally called a super-amide. The entire formulation was thoroughly mixed and milled. Some breakdown of the emulsion was noted after going through the mill, but it quickly recovered the original consistency with a small amount of stirring. A limited number of thermal shocks (140 F. overnight to 25 F. for three 8 hours) shows good stability. The pH of this formula was 6.40.

EXAMPLE 10 LEP solvent 30.0

Lanolin .3 Cetyl alcohol 1.6 Water 83.14 Carbitol 40.0 Propylene glycol 10.0 Dipropylene glycol methyl ether 20.0 Energetic W (polyoxyethylene alkyl phenol) non-lonic 6.0 Carbopol 934 1.4 Bentonite 2.0

TiO 2.0 Triethanolamine 2.34

This composition was prepared by the general process previously outlined and produced a 'good cleaning emulsion removing hecto ink quite easily, as well as rustoleum paint. It spreads well on the hand.

EXAMPLE 11 Percent Buyol 35 (a petroleum distillate similar to deodorized kerosene) 20.0 Lanolin 0.25 Coconut alkanolamide (non-ionic) (Sandrol 100 CG) 3.0 TiO 0.2 H 0 43.75 Carbitol 10.0 Diethylene glycol 10.0 Propylene glycol 10.0 Carbopol 934 1.0 Triethanolamine 1.60

This composition prepared according to the general process of this invention provided a good looking emulsion with excellent viscosity and texture. The pH was 7.80 and cleaning was excellent for hecto ink, printing ink, and oil soluble dyes.

EXAMPLE 12 Percent Mineral oil 35.0 Lanolin 0.25 Coconut alkanolamide 2.0 TiO 0.1 H 0 34.78 Carbitol 10.0 Diethylene glycol 10.0 Propylene glycol 5.0 Polytergent G-300 1.0 Carbopol 934 0.7 Triethanolamine 1.17

' This product presented a good nice and smooth cleanmg emulsion although stiif.

EXAMPLE 13 Percent Mineral oil 20.0 Lanolin 0.25 Ethofat 60/15 3.0 H 0 45 8 Carbitol 20.0 Propylene glycol 10.0 Carbopol 934 0.25 Oleyl sarcosine (Sarkosyl O) 0.25 Triethanolamine 0.43

This composition provided a good thin emulsion in the form of a lotion which flowed readily and was adaptable for use in a squeeze bottle and liquid dispensers.

EXAMPLE 14 Percent Kerosene 42.1

Ethylene oxide condensate of fatty acid amide (non-ionic) 5.3 Carbopol 0.7 H 47.7 Sodium hydroxide, 0.1 N 4.2

This composition prepared by the process of this invention showed good stability and no syneresis upon centrifuging. In addition 1% lanolin may be desirably added to the emulsion as well as other compatible agents.

As has been above described, various changes in the amounts of the materials required and substitution of known equivalents may be made in this invention according to the teachings theerof. In the employment of the basic four-component emulsion utilizing water, hydrocarbon solvent, neutralized hydrophilic acid polymer thickening agent, and the emulsifying agent, various changes may be made. For example, the percentage of hydrocarbon or organic solvent may vary. Likewise the emulsifying agent, which is preferably non-ionic when used with the copolymer mentioned, can be varied as typified in the examples. In addition to the basic four components mentioned above in the so-called waterless skin cleaner emulsion and as typified in the examples, additional agents may be employed to give desirable properties to'the composition, such as the'addition of emollients, such as lanolin, humectants, bacteriostatic agents such as hexachlorophene, perfume, color and the like, as will be well understood in the art. Such changes and modifications, as will be apparent to those skilled in the art, are in the spoce of this invention as defined \by the claims appended hereto.

What is claimed is:

1. A thixotropic skin cleaner having fast breaking qualities when massaged upon the skin and adapted to be used without the addition of water, comprising a liquid paraffinic hydrocarbon solvent for skin contaminants including grease, grime and dirt, a nonionic polyethylene oxide reaction product emulsifying agent, a synthetic hydrophilic acid polymer colloid at least partially neutralized in situ by an alkaline agent, said colloid being a copolymer of about 99% by weight of acrylic acid and about 1% by weight of a polyallyl sucrose, and water.

2. A thixotropic skin cleaner having fast breaking qualities when massaged upon the skin and adapted to be used without water, comprising a mineral oil solvent for skin contaminants including grease, grime and dirt, a nonionic polyethylene oxide reaction product emulsifying agent, a tertiary amine having one alkyl group and two polyoxyethylene groups in an amount not to exceed about 2%, a synthetic hydrophilic acid polymer colloid at least partially neutralized in situ by an alkaline agent, said colloid being a copolymer of about 99% by weight of acrylic acid and about 1% by weight of a polyallyl sucrose, and water.

3. A thixotropic skin cleaner emulsion having fast breaking qualities when massaged upon the skin and being adapted to be used without Water, which comprises mineral oil, a polyoxyethylene fatty acid ester having an alkyl group of 12 to 22 carbon atoms and in which the hydrophilic ethylene oxide chain is sparingly soluble in mineral oil, the ethylene oxide content being in the range of 2 to 20 mols per mol of ester, a small amount of a tertiary amine having one alkyl group in which the carbon atoms range between 12 to 22 in an amount not to exceed about 2%, a synthetic hydrophilic acid polymer colloid at least partially neutralized in situ by an alkaline agent, said colloid being a copolymer of about 99% by weight of acrylic acid and about 1% by weight of a polyallyl sucrose, and water, said emulsion being partially neutralized to a pH of 5 to 7 to match the pH of the users skin.

4. A thioxotropic skin cleaner emulsion having fast breaking qualities when masaged upon the skin and being adapted to be used without water, which comprises water, mineral oil, a polyoxyethylene fatty acid ester having an alkyl group of 12 to 22 carbon atoms and in which the hydrophilic ethylene oxide chain is sparingly soluble in mineral oil, a glycol evaporation retarding agent and an oleyl sarcosine corrosion inhibitor, a synthetic hydrophilic acid polymer colloid at least partially neutralized in situ by an alkaline agent, said colloid being a copolymer of about 99% by weight of acrylic acid and about 1% by weight of a polyallyl sucrose, said emulsion being partially neutralized to a pH of 5 to 7 to match the pH of the users skin.

5. A process for the preparation of skin cleaner emulsion having thixotr-opic and fast breaking qualities, which comprises dissolving an emulsifying agent in a water insoluble hydrocarbon solvent for magnet; and grease commonly found as contaminants in the skin, dissolving a synthetic hydrophilic acid polymer colloid in water, said colloid being at least partially neutralized in situ by an alkaline agent and being a copolymer of about 99% by weight of acrylic acid and about 1% by weight of a polyallyl sucrose, mixing the solvent and water preparations together with agitation, and adjusting the pH to the range of 5 to 7.

6. The process of claim 5 with the added step of adding oleyl sarcosine to the formulation, in quantities at least sufiicient to reduce corrosion by the formulation of metal receptacles in which 'it is contained.

7. A process for the preparation of skin cleaner emulsion having thixotropic and fast breaking qualities, which comprises dissolving a polyoxyethylene glycol fatty acid ester having an alkyl group of 12 to 22 carbon atoms and in a solvent for the grime, grease and dirt commonly found as contaminants in the skin, adding to said solution a tertiary amine in an amount not to exceed about 2%, dissolving in water a synthetic hydrophilic acid polymer colloid, said colloid being at least partially neutralized in situ by an alkaline agent and being a copolymer of about 99% by weight of acrylic acid and about 1% by weight of a polyallyl sucrose, mixing the solvent and water preparations together with agitation and adjusting the pH to the range of 5 to 7.

8. A process for the preparation of skin cleaner emulsion having thixotropic and fast breaking qualities, which comprises dissolving a polyoxyethylene glycol fatty acid ester having an alkyl group of 12 to 22 carbon atoms in mineral oil and adding thereto a small amount of a tertiary amine having one alkyl group and two polycxyethylene groups in an amount not to exceed about 2%, agitating said oil mixture with the application of heat, dissolving in Water a synthetic hydrophilic acid polymer colloid, said colloid being at least partially neutralized in situ by an alkaline agent and being a copolymer of about 99% by weight of acrylic acid and about 1% by weight of a polyallyl sucrose, with a corrosion inhibition agent and adding the same to said oil mixture with the ap plication of heat and agitation, and adjusting the pH to the range of 5 to 7.

9. A cleaner composition having fast breaking qualities, said cleaner being an oil in water emulsion consisting essentially of Water in a Water phase and a water insoluble hydrocarbon solvent for oil and grease contaminants in an oil phase, said water being present in a major proportion by weight, a nonionic organic emulsifying agent and a synthetic hydrophilic acid polymer colloid at least partially neutralized in situ by an alkaline agent, said colloid being present in a substantially smaller amount than any of the other components and consisting essentially of a copolymer of about 99% by weight of acrylic acid and about 1% by weight of a polyallyl sucrose, said composition having a pH of above 5 and less than 7.

10. The composition of claim 8, wherein the hydrocarbon solvent is a bland mineral oil, the emulsifier is a polyoxyethylene ester of a fatty acid having a carbon chain length of 12 to 22, dispersible but not completely soluble in water, the colloid being about 0.7-2.1% by Weight of the water, and the alkaline agent being sodium hydroxide,

11. A cleaner composition having fast breaking qualities, said cleaner being an oil in water emulsion consisting essentially of water in a water phase and a water insoluble hydrocarbon solvent for oil and grease contaminants in an oil phase, said Water being present in a major proportion by weight and said solvent being present in the amount of about 70% by weight of the water, a non-ionic organic emulsifying agent and a synthetic hydrophilic acid polymer colloid at least partially neutralized in situ by an alkaline agent, said colloid being present in the amount of about 1% by weight and consisting essentially of a copolymer of about 99% by weight of 'acrylic acid and about "1%" by' weight of a polyallyl sucrose, said composition having a pH of above 5 and less than 7.

12. A skin cleaner composition having fast breaking qualities, said cleaner being an oil in water emulsion consisting essentially of water in a water phase and a water insoluble hydrocarbon solvent for oil and grease contaminants in an oil phase, said water being present in a major proportion by Weight, an organic emulsifying agent and a synthetic hydrophilic acid polymer colloid at least partially neutralized in situ by an alkaline agent, said colloid being present in a substantially smaller amount than the oil and water components and consisting essentially of a oopolymer of about 99% by weight of acrylic 12 acid and about 1% by weight of a polyallyl sucrose, said composition having a pH of about 5 to 7.

13. A thixotropic skin cleaner having fast breaking qualities when massaged upon the skin and adapted to be used without the addition of water, comprising a liquid References Cited by the Examiner UNITED STATES PATENTS 2,109,842 3/1938 Harris 252118 2,410,168 10/1946 Kleinicke 252l 2,567,999 9/1951 Guastavino 252118 2,798,053 7/1957 Brown 252-89 OTHER REFERENCES Ethofats, Ethomids, Ethomeens, pub. of Armour Chemical Div., 1954, pp. 3, 15-17 relied on.

Lesser: Waterless Hand Cleaners, in Soap and Sanitary Chemicals, April 1948, pp. 48-50 and 181.

LEON D. ROSDOL, Primary Examiner.

ALBERT T. MEYERS, JULIUS GREENWALD,

Examiners. A. T. MEYERS, Assistant Examiner. 

2. A THIXOTROPIC SKIN CLEANER HAVING FAST BREAKING QUALITIES WHEN MASSAGED UPON THE SKIN AND ADAPTED TO BE USED WITHOUT WATER, COMPRISING A MINERAL OIL SOLVENT FOR SKIN CONTAMINANTS INCLUDING GREASE, GRIME AND DIRT, A NONIONIC POLYETHYLENE OXIDE REACTION PRODUCT EMULSIFYING AGENT, A TERTIARY AMINE HAVING ONE ALKYL GROUP AND TWO POLYOXYETHYLENE GROUPS IN AN AMOUNT NOT TO EXCEED ABOUT 2%, A SYNTHETIIC HYDROPHILIC ACID POLYMER COLLOID AT LEAST PARTIALLY NEUTRALIZED IN SITU BY AN ALKALINE AGENT, SAID COLLOID BEING A COPOLYMER OF ABOUT 99% BY WEIGHT OF ACRYLIC ACID AND ABOUT 1% BY WEIGHT OF A POLYALLYL SUCROSE, AND WATER. 